KR100886977B1 - One step hydroformylation and hydrogenation process for preparing a 1,3-propanediol - Google Patents

Abstract

(a) contacting a mixture of ethylene oxide, carbon monoxide, hydrogen, a non-water miscible reaction solvent and a hydroformylation catalyst composition; (b) heating the reaction mixture to yield a single phase reaction product mixture containing 1,3-propanediol, such that phase separation can be induced by temperature reduction; And (c) a temperature reduction in combination with the method of adding a phase cleavage inducing agent to the mixture, (ii) a temperature reduction in combination with the method of first adding a miscible cosolvent and then removing this miscible cosolvent, (Iv) adding a miscible cosolvent first, followed by removing the miscible cosolvent, and (iii) adding a phase cleavage inducing agent to the reaction product mixture. Inducing separation wherein phase separation comprises a first phase comprising most of the reaction solvent, at least 50 wt% of the catalyst composition, and unreacted ethylene oxide, and a second phase comprising most of the 1,3-propanediol A method for hydroformylation and hydrogenation of 1,3-propanediol, comprising the step represented by.

Ethylene oxide, 1,3-propanediol, hydroformylation, hydrogenation, phase separation

Description

ONE STEP HYDROFORMYLATION AND HYDROGENATION PROCESS FOR PREPARING A 1,3-PROPANEDIOL}

The present invention relates to a process for synthesizing aliphatic 1,3-diol, in particular 1,3-propanediol, in one step from ethylene oxide (hereinafter EO) and synthesis gas.

Aliphatic 1,3-diols, in particular 1,3-propanediol, have many uses as monomer units for polyesters and polyurethanes and as starting materials for the synthesis of cyclic compounds. For example, CORTERRA polymers are polyesters characterized by significant properties, made of 1,3-propanediol (hereinafter PDO) and terephthalic acid (CORTERRA is a trade name). There is a great deal of interest in the art to uncover new PDO synthesis pathways that demonstrate efficient, economical and methodological advantages.

U.S. Pat.Nos. 3,463,819 and 3,456,017 describe the use of tert-phosphine modified cobalt carbonyl catalysts for hydroformylation of ethylene oxide to produce 1,3-propanediol and 3-hydroxypropanal (hereafter 3-HPA). Teach US Patent No. 3,687,981 discloses a PDO synthesis method. In this method, phase separation of the intermediate hydroxyethyl hydroxy dioxane occurs at room temperature or lower, before the material is hydrogenated into the product. US Patent No. 5,256,827; 5,344,993; 5,459,299; 5,463,144; 5,463,145; 5,463,146; 5,545,765; 5,545,766; 5,545,767; And 5,563,302, 5,689,016 (all transferred to Shell) initiate cobalt-catalyzed hydroformylation of ethylene oxide.

U.S. Pat.No. 5,304,691 (cello assigned) discloses ethylene oxide (EO), di-tert-phosphine modified cobalt carbonyl catalyst, ruthenium catalyst promoter, and synthesis gas (carbon monoxide and hydrogen) under hydroformylation reaction conditions in an inert reaction solvent. ), A method of hydroformylation of ethylene oxide with 3-hydroxypropanal and 1,3-propanediol is disclosed. The patent suggests that reducing the temperature of the reaction product mixture will cause phase separation. However, this is not always the case, and it has been found that under some preferred operating conditions, phase separation hardly occurs due to temperature reduction. In such cases, expensive liquid-to-liquid extraction or distillation methods are required to separate the materials.

Applicant has clearly shown a process in the art as a one-step hydroformylation and hydrogenation process for synthesizing PDO, in which phase separation can be carried out as a single phase under conditions which cannot be induced by temperature reduction alone without the use of the present invention. found. The PDO product can be separated from the reaction solvent without using expensive extraction or distillation methods, ie it is possible for the expensive hydroformylation catalyst to be recycled without exposure in the decomposition or downstream processing. In addition, residual EO in the crude PDO product can be converted by using the product itself as the reaction solvent, and heavy ends (undesired by-products heavier than PDO) may be removed from the system with minimal impact on the catalyst. As such, the method of the present invention is very efficient and exhibits greater flexibility in processing.

Summary of the Invention

The present invention is a one-step hydroformylation and hydrogenation method of 1,3-propanediol, comprising the following steps:

(a) contacting a mixture of ethylene oxide, carbon monoxide, hydrogen, a non-water miscible reaction solvent and a hydroformylation catalyst composition in a reactor;

(b) at a pressure in the range from 0.7 to 27.6 MPa (100 to 4000 psi), for a time effective to yield a single phase reaction product mixture containing 1,3-propanediol, in the range from 30 to 150 ° C. Heating to temperature; And

(c) reducing the temperature in combination with the method of adding a phase cleavage inducing agent to the mixture in an amount sufficient to induce phase separation, and (ii) first adding a miscible cosolvent to maintain the reaction product mixture as a single phase. Temperature reduction in combination with the method of removing this miscible cosolvent, and (i) first adding a miscible cosolvent to maintain the reaction product mixture as a single phase, and then removing this miscible cosolvent. And (iii) inducing phase separation in at least one method selected from the group consisting of adding a phase cleavage inducing agent to the reaction product mixture in an amount sufficient to induce phase separation. A majority of the solvent, at least 50 wt% of the catalyst composition, and a first phase comprising unreacted ethylene oxide and a second phase comprising most of the 1,3-propanediol.

The method can be carried out when the second phase also contains a catalyst, a reaction solvent, and a high molecular weight by-product. This method may therefore involve the induction of phase separation followed by physical separation of the two phase mixtures. The method may further comprise directly recycling the first phase to step (a) for further reaction with previously unreacted starting material. The method also includes extracting a residual catalyst from the second phase, recycling the catalyst to step (a), and sending the remaining second phase containing 1,3-propanediol to the recovery device. It may further include. The recovery device for 1,3-propanediol may be a distillation column that separates the 1,3-propanediol product from high molecular weight by-products. The method further comprises separating the light solvent from 1,3-propanediol, distilling to separate into individual light solvents, and optionally recycling the individual light solvents to step (a). can do.

1 is a schematic diagram of a method design of the present invention, including several optional design features.

In the present invention, Applicant has made some surprising findings and incorporated them into a novel one-step hydroformylation and hydrogenation method for synthesizing PDO, demonstrating many advantages over any of the methods currently available in the art. If recycling of the reaction solvent and catalyst is required in the present invention, this can be achieved without excessive formation of miscible byproducts. In addition, the residual EO and catalyst partitioned into separated products can be reacted to convert EO to a product.

These advantages are obtained in the present invention, and further improvements can be obtained by the following method:

1. Method using a medium polar solvent as reaction solvent.

2. While recovering most of the EO discharged from the reactor to recycle to the reaction zone, the EO may be kept between 0.2 and 20 wt% to maintain a fast reaction rate and minimize commercial reactor costs. To improve yield by recycling.

3. A process using one or more liquid phase separations / extractions to facilitate the recycling of EO and most importantly to enrich one liquid phase in the PDO relative to the catalyst. The process arrangement of the present invention allows for more efficient separation of PDOs through heat recovery with less stress on the catalyst. This method also allows significant proportions of the catalyst to be recycled on the PDO depleted reaction solvent, while avoiding thermal stress completely. The method also allows for removal streams to be generated from the bottom of the PDO rich stream after heat recovery. The cracked catalyst is expected to accumulate in this polar phase, thereby allowing selective removal of only cracked catalysts comprising reactor by-products that are heavy relative to the entire catalyst list, ie the use of very expensive bonded hydroformylation catalysts. Can be minimized.

4. Continuous hydroformylation of the EO fraction discharged with the PDO rich phase compared to the discharge with the PDO deficient reaction solvent phase provides a means to improve EO yield without requiring thermal recycle / distillation of the EO. can do. Thermal recirculation / distillation of EO may present a safety hazard. That is, liquid-liquid phase separation can be used with continuous hydroformylation of the EO fraction withdrawn with the PDO rich stream to recycle most of the EO.

5. A method of reextracting the PDO rich phase under synthesis gas to further enhance catalyst and EO recycle (using a moderately polar reaction solvent prepared).

The present invention therefore provides a very simplified method of carrying out the preliminary separation of PDO from the recycle catalyst and reaction solvent, ie concentrating the desired PDO product prior to the final purification step. This method utilizes direct separation of the product rather than the introduction of a liquid extractant which has to be subsequently removed through the added distillation capacity. This more direct route lowers energy intensity and saves the capital needed. In addition, the catalyst separated from the PDO and recycled in this phase cleavage manner is not subjected to stress associated with thermal evaporation, distillation, or recovery through liquid extraction means.

Using the process of the present invention, catalytic cracking is kept to a minimum because not only does the thermal stress as in distillation use apply, but also the entire catalyst list does not go through the extraction step. Removal from the system of heavy bottoms or by-products can now be achieved with minimal impact on the catalyst. With the concept of "final reaction" for the crude PDO product, it is possible to increase the EO concentration, so that the reaction rate can be increased.

The figure is a schematic of the method of the invention. Bubble column or stirred autoclave, in which the separation, mixing, or staged stream of ethylene oxide (1), synthesis gas [CO / H ₂ ] (2), and catalyst (3) are operated in batch or continuous mode Filled into a hydroformylation reactor (4), which may be a pressure reactor such as. By conducting the reaction to yield the target concentration of PDO, partitioning of the reaction mixture can be induced by a temperature decrease in the range of about 0 to 90 ° C. The reaction mixture from reactor 4, which is at a temperature of about 80 ° C., is in one aspect passed through line 5 to cooler 6, which is preferably a heat exchanger, cooled to about 45 ° C., and then weir Transfer to an unheated settler or separator 8, which may be a vessel, mixed-precipitator, filter bed coalescer or similar vessel. Partitioning and precipitation can be carried out at a pressure between the reaction pressure and the ambient pressure, preferably at the reaction pressure, and will require a residence time of approximately 30 minutes or less. After partitioning and precipitation of the reaction mixture, the phase (shown as the top phase) containing mainly the reaction solvent, unreacted ethylene oxide, and most of the catalyst was recycled to the reactor via line 18. The PDO rich phase (shown as the bottom phase) containing a small amount of reaction solvent and a small amount of by-product and heavy bottoms (relative to the product) is transferred via line 9 to the splitter column 10 where the light solvent is reactant. Separated overhead for selective recycling of the furnace. Bottom 13 of cleavage column 10, containing PDO and residual catalyst, is directed to column 18 to separate the PDO product 19 overhead from the high molecular weight by-product exiting 20. Alternatively, the bottom 13 of the splitter column 10 is directed to an optional catalyst extractor 14.

The figures also show some optional features in the method design. In a high cost catalyst system, as an optional member of the present invention, a catalyst extractor 14 capable of recovering a small amount of catalyst discharged with the product rich phase is included. In this configuration, the fresh or recycled reaction solvent 27 supplied through 15 is crude PDO in the extractor 14 which promotes intimate liquid-liquid contact through the use of trays, packings, or forced stirring. Flowing backwards with the product 13 causes the reaction solvent to extract the active catalyst from the crude PDO product. The recovered catalyst is then contained in the prepared reaction solvent stream and returned to main reactor 4 via line 16. In addition, the optional flasher other than the heat exchanger (cooler 6) before the separator 8 is indicated by 23. An optional stream for introducing a phase fission inducer is indicated at 24. Optional members for inducing and maintaining phase breakdown begin with a heat exchanger (cooler) that reduces the temperature of the hydroformylation product stream, so that phase breakdown will occur under certain conditions. The optional flasher 23 can be used to remove previously added miscible cosolvents to induce phase cleavage. Miscible cosolvents may include, for example, short chain alcohols. In stream addition 24, a small amount of phase cleavage inducing reagent is optionally added to induce phase cleavage following hydroformylation. Phase cleavage inducers will be substances which change the polarity of the mixture and may include, for example, water or straight alkanes such as hexane, heptane or dodecane. Stream 25 is a selective recycle of additives leading to phase cleavage, stream 27 represents the separation and recycling of MTBE, and stream 28 represents the separation and recycling of additional light solvent.

Through any combination of phase cleavage configurations, a PDO rich product phase and a recycle reaction solvent rich phase are obtained from the phase cleavage unit 8. As mentioned above, the reaction solvent containing most of the unreacted EO and most of the catalyst is easily recycled to the hydroformylation reaction via line 16. Data showing the preferred recycling of EO and catalyst are presented in Table 2. The PDO rich phase (shown as the heavier phase) from the phase splitting unit 8 is sent to a heat recovery zone comprising a splitter column 10, a product column 18, and a reaction solvent column 12. In the product column 18, the PDO is separated into overheads 19, with heavy bottoms and some residual catalyst being withdrawn from product column 18 through distillation or evaporator bottoms 20. The data provided as the "% Total" columns of Tables 2 and 4 show that only one fraction of the catalyst is partitioned into the PDO rich phase. This allows the heavy bottoms to be removed via the removal stream 26 while losing significantly less catalyst than is possible in other configurations. That is, one step loss of expensive catalysts is substantially reduced. In addition, the catalyst removed with the bottoms after distillation of the PDO rich phase is preferably rich in the degraded catalyst to be removed from the system, while the active catalyst is preferably recycled with the reaction solvent rich phase.

A disadvantage of the selection member 23 which requires a preflash before phase splitting is that the amount of EO that can be easily recycled is reduced and the pressure must be reduced before flash distillation. Another optional member allows to maintain high pressure during the phase split and recycle steps, which minimizes the need for pumping. The addition of a small amount of phase cleavage inducer after hydroformylation, indicated at 24, may be helpful. The phase fission inducer is mainly discharged with the PDO rich phase and will be recovered in the distillation zone, so that it can optionally be recycled to resume phase fission.                 

As mentioned above, the addition and subsequent removal of miscible cosolvents is one of the optional members controlling the phase cleavage method. Suitable miscible alcohols and admixtures include, for example, short chain alcohols such as methanol, ethanol, and isopropanol. For example, in order to bring the PDO product to the desired concentration at the reaction temperature, one cosolvent, such as ethanol, can be added as necessary with an appropriate bulk solvent. The cosolvent may be used in an amount to induce solubility, typically in an amount of 1 to 50 wt%, preferably 2 to 20 wt%, most preferably 5 to 20 wt% of the total reaction product mixture.

In the process of the invention shown in FIG. 1, as described below, an oxirane of 10 carbon atoms, preferably 6 carbon atoms or less, specifically ethylene oxide (EO), is present in the hydroformylation catalyst complex of a specific group. Can be converted to their corresponding 1,3-diol via hydroformylation reaction together with synthesis gas.

The 1,3-diol may be prepared by the synthesis of oxirane, catalyst, selective cocatalyst and / or catalyst promoter and reaction solvent under hydroformylation conditions (preferably between 1: 1 and 8: 1, preferably between 2: 1 and 6). By filling into a pressure reactor with the introduction of a: 1 molar ratio of hydrogen and carbon monoxide mixture).

The process of the invention can be carried out in a batch process, in a continuous process, or in a mixture of these, but the nature of the invention allows the continuous one-step method to operate more efficiently and efficiently than previously possible. The process of the invention can be carried out in continuous mode by maintaining the homogeneity of the reaction mixture until the maximum PDO concentration is reached. Reaction conditions that allow this mode of operation include the concentration of EO in the reaction mixture that is at least about 0.5 wt%, and the prevention of by-product formation such as light alcohol and acetaldehyde, or the use of a flash step to remove the by-product. The reaction of adding EO stepwise to two to four reactors is preferred for continuous operation.

The reaction method includes converting EO to PDO via 3-hydroxypropanal intermediate, which is hydrogenated to PDO in situ after formation. As used herein, "in situ" means that the conversion of ethylene oxide to PDO is performed in the presence of a single catalyst system for both hydroformylation and hydrogenation, without separation of the 3-hydroxypropanal intermediate. The reaction is carried out under conditions effective to yield a reaction product mixture containing relatively small amounts of 3-hydroxypropanal (HPA), acetaldehyde and heavy bottoms and PDO in the desired maximum concentration range.

For best results, the method is carried out under elevated temperature and elevated pressure conditions. The reaction temperature is in the range of ambient temperature to 150 ° C, preferably 50 to 125 ° C, and most preferably 60 to 110 ° C. The reaction pressure (total pressure, or partial pressure if inert gas diluent is used) is preferably in the range of 5 to 15 MPa, more preferably 8 to 10 MPa. In the batch process, the reaction is generally completed in 1.5 to 5 hours.

The reaction solvent is preferably inert, meaning that it is not consumed during the reaction process. Ideally, the reaction solvent in the process of the present invention dissolves the feedstock and the product during the course of the reaction, but reducing the temperature causes phase separation. Since the ideal reaction solvent exhibits low to moderate polarity, PDO (which is calculated and converted in situ) will remain in solution during the reaction process but will readily split into separate phases upon cooling. Suitable reaction solvents are described in US Pat. No. 5,304,691, which is incorporated herein by reference in its entirety. Good results can be obtained by using ethers comprising cyclic and acyclic ethers, optionally ethers in combination with alcohols or aromatic hydrocarbons.

One group of suitable reaction solvents are alcohols or ethers which may be described by the formula:

R ₂ -OR ₁

Wherein R ₁ is hydrogen or C _1-20 linear, branched, cyclic or aromatic hydrocarbon group or monoalkylene oxide or polyalkylene oxide, R ₂ is C _1-20 linear, branched, cyclic or aromatic Hydrocarbon group, alkoxy group, monoalkylene oxide or polyalkylene oxide. Preferred reaction solvents are those solvents which can be described by the formula:

Wherein R ₁ is hydrogen or a C _1-8 hydrocarbon group, and R ₃ , R ₄ , and R ₅ are independently selected from C _1-8 hydrocarbon groups, alkoxy groups, or alkylene oxides. Such ethers include, for example, methyl-tert-butyl ether, ethyl-tert-butyl ether, diethyl ether, phenylisobutyl ether, ethoxyethyl ether, diphenyl ether, and diisopropyl ether, among others Methyl-tert-butyl ether.

The EO will preferably be maintained during the reaction at a concentration of at least about 0.2 wt%, generally in the range of 0.2 to 20 wt%, preferably in the range of 1 to 10 wt%, based on the total weight of the reaction mixture. The process of the present invention can be carried out in a continuous mode while maintaining the EO concentration, for example, via stepwise EO addition.

Catalysts useful in the construction of a one-step method of the present invention include intrinsically uncoupling cobalt carbonyl compounds, and optionally, phosphine ligands, coordinator or polydentate N-heterocyclic ligands, porporin ligands, or phospholars. And a homogeneous specific dimetallic catalyst comprising a second Group VIII metal component selected from ruthenium or iron compounds bound to a ligand selected from noalkanes ligands.

Suitable cobalt source materials also include salts that have been reduced to zero valences by heat treatment in hydrogen and carbon monoxide atmospheres. Examples of such salts include, for example, cobalt salts of inorganic acids such as chlorides, fluorides, sulfates, sulfonates, and the like, as well as carboxylic acid cobalt such as acetates, octanates, and the like, which are preferred. Mixtures of these cobalt salts can also be used. However, when using a mixture, it is preferred that at least one of the components of the mixture is cobalt alkanoic acid of 6 to 12 carbon atoms. The reduction may be carried out before the use of the catalyst and may be achieved simultaneously with the hydroformylation process in the hydroformylation zone.

Preferred catalysts include cobalt components and binding ruthenium compounds that are essentially non-bonding. These catalyst complexes can be identified by absorption peak characteristics in the infrared spectrum of the catalyst composition. Ruthenium may bind with diphosphine ligands, polydentate or bidentate N-heterocyclic ligands, or the bis (phospholano) alkane ligand class.

The catalyst can be prepared by a stepwise method or a self-bonding method which will be discussed later.

When the ligand is an N-heterocyclic ligand, many N-heterocyclic compounds are identified as suitable ligands for one step PDO synthesis using cobalt-ruthenium catalyst pairs. Suitable coordinating or polydentate N-heterocyclic ligands include, but are not limited to, the following ligands: diazines such as pyrimidine, pyrazine, pyridazine, as well as benzodiazines such as quinazoline And quinoxaline; Bispyridine, such as 2,2'-dipyridyl (DIPY), 2,2'-bipyrimidine (BPYM), 1,10-phenanthroline (PHEN), di-2-pyridyl ketone, 4,4 '-Dimethyl-2,2'-dipyridyl, 5,6-dimethylphenanthroline, 4,7-dimethylphenanthroline, 2,2'-biquinoline, neocouproin, and 2,2'- Dipyridylamine; Multipyridine such as 2,4,6-tripyridyl-sec-triazine (TPTZ), 3,6-di-2-pyridyl-1,2,4,5-tetrazine, 2,2 ', 6 ', 2'-terpyridine, 2,3-bis (pyridyl) pyrazine, and 3- (2-pyridyl) -5,6-diphenyl-1,2,4-triazine; pyridine, 3-hydric Low-cost analogs derived from oxypyridine, and quinoline, especially col-tar extracts; and certain 2,6-pyridyldiimines such as 2,6-bis (N-phenyl, methylimino) pyridine, and 2,6- Bis [N- (2,6-diisopropylphenyl) methylimino] pyridine.

Preferred heterocyclic compounds for use as ligands include 2,2'-dipyridyl (DIPY), 2,2'-bipyrimidine (BPYM), and 2,4,6-tripyridyl-sec-triazine (TPTZ) is included. The structure of these three N-heterocyclic compounds is as follows:

N-heterocyclic binding ruthenium and cobalt counter ions for best results are characterized by cobalt tetracarbonyl anions exhibiting a characteristic cobalt carbonyl IR band in the 1875 to 1900 cm ⁻¹ region, especially the 1888 cm ⁻¹ region ( [Co (CO) ₄ ] ^- ).

When ruthenium binds to phospholanoalkanes, suitable phospholanoalkanes include phosphoran substituted alkanes compounds of Formulas I and II as follows:

In both of formulas (I) and (II), R is lower alkyl, trifluoromethyl, phenyl, substituted phenyl, aralkyl, or ring substituted aralkyl; n is an integer from 1 to 12; In formula (II), A is CCH ₃ , CH, N, or P. Preferred compounds are compounds of formula I and II, wherein R is lower alkyl and C is ₁ to C ₆ alkyl and n is 1 to 3. Most preferred are compounds of formulas I and II, wherein R is methyl and n is 1-3.

Examples of such compounds include 1,2-bis (phospholano) ethane; 1,2-bis (2,5-dimethylphospholano) ethane; 1,2-bis [(2R, 5R) -2,5-dimethylphospholano] ethane; 1,2-bis [(2S, 5S) -2,5-dimethylphospholano] ethane; 1,3-bis (2,5-dimethylphospholano) propane; Tris [(2,5-dimethylphospholano) methyl] methane; Tris [(2,5-dimethylphospholano) ethyl] amine; Or 1,1,1-tris [(2,5-dimethylphospholano) ethyl] ethane. Particularly useful compounds are, for example, 1,2-bis [(2R, 5R) -2,5-dimethylphospholano] ethane (BDMPE), 1,2-bis [(2S, 5S) -2,5-dimethyl Bidentate bis (phospholano) alkanes such as phospholano] ethane, racemic mixtures of these two compounds, and 1,2-bis (porpolano) ethane.

Cobalt tetracarbonyl anions ([Co (CO) ₄ ] ^- ) are also believed to be phospholanoalkanes ligands and counter ions for best results. However, in active catalysts these ions may be in modified form.

A highly effective catalyst system used in Examples 1-14 to illustrate the phase cleavage method design of the present invention is a ruthenium oxide metal bound by tert-diphosphine ligand, preferably having a non-bonding cobalt compound as counter ion. Ruthenium modified catalyst characterized in that.

The phosphorus ligand is tert-diphosphine of the formula:

RRP-Q-PR'R '

Wherein each functional group R and R 'is independently or collectively a hydrocarbon residue of up to 30 carbon atoms and Q is an organic bridge group of 2 to 4 atoms in length. When functional group R or R 'is monovalent, it may preferably be alkyl, cycloalkyl, bicycloalkyl or aryl with up to 20 carbon atoms, more preferably up to 12 carbon atoms. Alkyl and / or cycloalkyl groups are preferred. The functional group Q is preferably composed of carbon atoms which can form part of a ring system such as a benzene ring or a cyclohexane ring. Q is more preferably an alkylene group having 2, 3 or 4 carbon atoms in length, most preferably 2 carbon atoms in length. A non-limiting example list of this diphosphine class includes 1,2-bis (dimethylphosphino) ethane; 1,2-bis (diethylphosphino) ethane; 1,2-bis (diisobutylphosphino) ethane; 1,2-bis (dicyclohexylphosphino) ethane; 1,2-bis (2,4,4-trimethylpentylphosphino) ethane; 1,2-bis (diethylphosphino) propane; 1,3-bis (diethylphosphino) propane; 1- (diethylphosphino) -3- (dibutylphosphino) propane; 1,2-bis (diphenylphosphino) ethane; 1,2-bis (dicyclohexylphosphino) ethane; 1,2-bis (2-pyridyl, phenylphosphanyl) benzene; 1,2-bis (dicyclopentiphosphino) ethane; 1,3-bis (2,4,4-trimethylpentiphosphino) propane; 1,2-bis (diphenylphosphino) benzene and the like. These functional groups R and R 'may be substituted with non-hydrocarbon groups themselves. In addition, both functional groups R and / or both functional groups R 'may form a ring such as phosphacycloalkane of 5 to 8 atoms with the phosphorus atom. Examples of 5-ring systems [phospholano ligands] include 1,2-bis (phospholano) ethane, 1,2-bis (2,5-dimethylphospholano) benzene, optionally pure (R, R ), (R, S), (S, S) -1,2-bis (2,5-dimethylphospholano) ethane or racemic mixtures thereof. The ring itself may be part of a multiple ring system. Examples of such ring systems can be found in the aforementioned '691 patent and WO-A-9842717, which are hereby incorporated by reference in their entirety. The former describes phosphabicyclononyl groups and the latter describes adamantyl functional groups, in particular phosphatrioxatricyclodecyl groups. Preferred are diphosphines in which both functional groups R and R 'together with the phosphorus atom form a ring. Most preferred ligands are 1,2-P, P'-bis (9-phosphabicyclo [3.3.1] and / or [4.2.1] nonyl) ethane [hereafter B9PBN-2], 1,2-P thereof , P'-propane and / or 1,3-P, P'-propane analogs thereof (hereafter B9PBN-3).                 

Di-tert-phosphine ligands are commercially available. Catalysts prepared therefrom are known in the art and their preparation methods are described in detail in US Pat. Nos. 3,401,204 and 3,527,818, which are incorporated herein by reference in their entirety. Phosphine ligands can also be partially oxidized in the manner described in the '691 patent to become oxidized phosphines.

The ratio of phosphine ligand to ruthenium atom is 2: 1 to 1: 2, preferably 3: 2 to 2: 3, more preferably 5: 4 to 4: 5, and most preferably about 1: 1. It can vary. It is assumed that this would be a tert-diphosphine ruthenium tricarbonyl compound, but it could also be a bis (tert-diphosphine ruthenium) pentacarbonyl compound. Unbound ruthenium carbonyl is believed to be an inactive species and therefore is intended to bind each ruthenium atom in catalyst preparation.

The counter ion for the best results is believed to be cobalt tetracarbonyl ([Co (CO ₄ ) ^- ]), but in an active catalyst this ion may be in its modified form. Some of the cobalt compounds can be modified using (excess) tert-diphosphine, for example up to 75 mol%, such as up to 50 mol%. However, the counter ion is preferably the non-bonded cobalt tetracarbonyl described above. Cobalt Carbonyl is Jay. By reacting the synthesis gas with a starting cobalt source, such as cobalt hydroxide, as described in J. Falbe's "Carbon Monoxide in Organic Synthesis" (Springer-Verlag, NY (1970)). It can manufacture.

The oxidation state of ruthenium atoms is not entirely certain (in theory, ruthenium can have valences from 0 to 8), which can also change during the hydroformylation process. Thus, the molar ratio of ruthenium to cobalt can vary within a relatively wide range. Sufficient cobalt (0) must be added to completely oxidize the entire complexed ruthenium used. Excess cobalt can be added, but no specific value is set. Suitably, the molar ratio varies from 4: 1 to 1: 4, preferably from 2: 1 to 1: 3, more preferably from 1: 1 to 1: 2.

The reaction mixture will preferably include a catalyst promoter to accelerate the reaction rate. Suitable promoters include monovalent and multivalent metal cation sources of weak bases such as alkali metal, alkaline earth metal, and rare earth metal salts of carboxylic acids and tert-amines. The promoter will generally be present in an amount ranging from about 0.01 to about 0.6 mol per mol of cobalt. Suitable metal salts include acetates, propionates, octates of sodium, potassium, and cesium; Calcium carbonate and lanthanum acetate. In view of its availability and the proven acceleration for ethylene oxide conversion, preferred promoters are dimethyldodecylamine and triethylamine.

The homogeneous dimetallic catalysts described can be prepared by the stepwise method described below. It is also within the scope of the present invention to prepare catalyst composites by a self-bonding method, in which all catalyst components are bound together simultaneously, but the conditions, in particular the solvent, are more likely to form bound ruthenium species than the bound cobalt species. Is chosen to be.

In the stepwise method, the first binding ruthenium component is prepared, and then the cobalt carbonyl component and any promoter are added to the ruthenium complex solution. Ruthenium complexes are formed by reacting ruthenium carbonyl, such as triruthenium dodecacarbonyl, with stoichiometric amounts of selected ligands. The reaction is carried out in a solvent capable of dissolving any catalyst intermediates. The solution is heated under a carbon monoxide atmosphere to a temperature within the range of about 90 to about 130 ° C., preferably about 100 to about 110 ° C., for a time sufficient to complete the reaction of ruthenium with the ligand, typically about 1 to about 3 hours. do. The selected cobalt carbonyl and any promoter to be used are then added to the solution of bound ruthenium carbonyl and the solution is held at elevated temperature for about 15 to about 60 minutes.

In the self-bonding method, careful selection of catalyst precursor and catalyst preparation solvent is important for obtaining the desired final catalyst composition. It is essential that the ligand binds to ruthenium carbonyl before the reduction produces any cobalt (0) carbonyl. Self-bonding catalyst preparation is carried out in a solvent by combining a cobalt salt such as cobalt octanoate, ruthenium (0) carbonyl such as triruthenium dodecacarbonyl, and a ligand for ruthenium. The starting component is present in a Co: Ru ratio in the range of about 1: 0.15 to about 1: 2, preferably in a ratio of 1: 2, and in a Ru: ligand ratio in the range of about 1: 0.16 to about 1: 1. The solution is heated under a reduced atmosphere, such as 1: 4 CO: H ₂ , to a temperature in the range of about 110 to about 130 ° C. for a time effective for the ruthenium to be essentially complete, typically about 1 to about 3 hours. do.

The optimal ratio of oxirane feedstock to dimetallic catalyst complex will depend in part on the specific complex used. However, the molar ratio of oxirane to cobalt in the catalyst complex is generally satisfactory when 2: 1 to 10,000: 1, with a molar ratio of 50: 1 to 500: 1 being preferred.

The product mixture resulting from the hydroformylation reaction of the present invention is preferably recovered by phase separation and then subjected to several distillation steps to recycle the unreacted starting materials as well as the catalyst and reaction solvent for further use. . The present invention provides a commercially available process that involves efficient cycles of catalyst recovery and several cycles of essentially complete recycling of the catalyst to the reaction. Preferred catalyst recovery methods involve the separation of the two liquid phase mixtures as described above, and recycling to the reactor in the bulk reaction solvent phase, including recovery of at least 60 to 90 wt% of the initial catalyst.

In a preferred manner of carrying out the process, reaction conditions such as oxirane concentration, catalyst concentration, reaction temperature and the like are obtained by obtaining a homogeneous reaction mixture at elevated temperature, and upon cooling of the mixture, the reaction mixture comprises a reaction solvent phase containing most of the catalyst. It is selected such that it can be fractionated into a second phase containing most of the 1,3-propanediol. This partitioning facilitates separation and recovery of the product, recycling of the catalyst, and removal of heavy bottoms from the reaction solvent system. This method is referred to as the phase separation catalyst recycle / product recovery method.

In the process of the invention, the reactor contents are transferred to a suitable vessel which is precipitated or at a pressure which is at or close to the reaction pressure, where upon cooling lightly or to a significant extent, they are substantially different and are substantially rich in product or catalyst and reaction. Separate phases are formed that are significantly rich in solvent. The phase rich in catalyst and reaction solvent is directly recycled for further reaction with the feedstock. The product is recovered from the product rich phase using an easy method.                 

It is important to run the reaction so that the diol product maintains a concentration level in the reaction mixture suitable for phase separation. Preferably, the concentration of 1,3-propanediol is 1 to 50 wt% of the total reaction product mixture. More preferably, the concentration of 1,3-propanediol is 8 to 32 wt% of the total reaction product mixture. Most preferably, the concentration of 1,3-propanediol is 16 to 20 wt% of the total reaction product mixture.

The temperature during the static precipitation of the bed may be between just above the freezing point of the reaction mixture and at least 10 ° C. lower than the reaction temperature. Preferably, the temperature during phase separation is reduced to 10-100 ° C., and more preferably 10-40 ° C., depending on the reaction temperature. Preferably, the temperature during phase separation may be 27 to 97 ° C, most preferably 37 to 47 ° C.

EO concentration is maintained to prevent the formation of light alcohols and aldehydes that are admixtures. The oxirane is preferably at least about 0.2 wt% of the total reaction product mixture, generally in the range of 0.2 to 20 wt% of the total reaction product mixture, preferably in the range of 1 to 10 wt% of the total reaction product mixture during the reaction. Will remain at concentration.

The reaction can be run in a two phase system. However, yield and selectivity are maximum when there is a high concentration of product in the single phase reaction and subsequent phase separation immediately upon cooling.

In addition to the temperature decrease, the partitioning of the reaction mixture can be facilitated by the addition of a phase cleavage inducing agent. Such inducers will be added to the reaction mixture in amounts ranging from about 2 to 20 wt%, preferably from 2 to 10 wt%, and most preferably from 4 to 8 wt%, based on the total reaction mixture. Suitable inducers include, but are not limited to, glycols such as ethylene glycol and straight chain alkanes such as hexane and dodecane.

The optimal amount of each phase inducing agent will vary and can be determined by routine experimentation. For example, hexane leads to reaction mixture partitioning when present in a methyl-tert-butyl ether reaction solvent at a concentration of about 16 wt% based on the total reaction solvent. Therefore, the primary reaction solvent and any phase inducing agent will affect the partitioning action of the reaction mixture.

Partitioning can be achieved by adding PDO to the reaction mixture to reach product concentration to the desired ratio. In addition, miscible alcohols and admixtures of similar polarity, such as ethanol, propanol and isopropanol, can be initially added (miscible cosolvents), then removed in advance, followed by phase separation. For example, under normal reaction conditions, a homogeneous PDO concentration of about 16 wt% in the methyl-tert-butyl ether reaction solvent at about 70 ° C. immediately reduces the temperature to about 43 ° C., causing the reaction mixture to react to the reaction solvent rich phase. And PDO enrichment. Ethanol promotes partitioning of the reaction product mixture at concentrations in the range of about 5 to about 8 wt%.

Commercial operation will require several cycles and efficient catalyst recovery to essentially recycle the catalyst to the reaction. Preferred catalyst recovery methods involve the separation of the two liquid phase mixtures as described above, and recycling to the reactor in the bulk reaction solvent phase, including recovery of at least 60 to 90 wt% of the initial catalyst.

The following examples will be provided to further illustrate the invention disclosed herein. The examples are merely illustrative and are not to be construed as limiting the scope of the invention in any way. Those skilled in the art will recognize many possible variations without departing from the spirit of the disclosed invention.

Table 1 lists the categories of materials, formulations, and abbreviations used in the examples.

Materials and Formulations Co source material CoOc DCO Octane cobalt dicobalt octacarbonyl Ru source material TRC BRCC Triruthenium dodecacarbonyl bis (ruthenium tricarbonyl chloride) Ligand B9PBN-2 BDEPE BDIPE BDOPE BDMPE 1,2-P, P'-bis (9-phosphacyclocyclononyl) ethane 1,2-bis (diethylphosphino) ethane 1,2-bis (diisobutylphosphino) ethane 1,2-bis ( 2,4,4-trimethylpentylphosphino) ethane (R, R) -1,2-bis (dimethylphospholano) ethane Reaction solvent MTBE T / CB Methyl-tert-butyl ether 5: 1 v / v mixture of toluene / chlorobenzene Oxirane EO Ethylene oxide accelerant DMDA NaAc Dimethyldodecylamine sodium acetate

Example 1

Phase separation catalyst recycle / product recovery method using a catalyst formed by self-bonding.

1.85 g (5.35 mmol Co) ethyl cobalt (II), 1.392 g (4.48 mmol) ethane, 1,2-bis (9-phosphacyclononyl) ethane, triruthenium dode 0.509 g (2.3 mmol Ru) of silcarbonyl, 145.85 g of methyl-tert-butyl ether [MTBE] and 0.30 g of dimethyldodecyl amine were added. The autoclave body was sealed and mounted on a bench scale processing unit. Under a headspace of 4: 1 H ₂ : CO ratio synthesis gas at 1500 psi (10.3 MPa), the mixture was equilibrated for 2 hours at 130 ° C. and the catalyst was preformed. The reactor temperature was reduced to 90 ° C. 16.96 g of ethylene oxide (EO) were added to react with the synthesis gas feedstock in a 2: 1 H ₂ : CO ratio until EO was consumed substantially but not completely. The reactor contents were transferred to a phase separator under reaction conditions, where the phase separation started immediately. From the vessel, 12.94 g of the underlying material was separated. The reaction liquid in the upper layer was recycled to the reactor. The compositions of the upper and lower layers are listed in Table 2. Catalyst compartmentalization data is shown in Table 3. The 1,3-propanediol product was calculated at an average rate of 20 g / L / hour.

Example 2

Phase separation method, recirculation 1.

The reaction solution recycled from Example 1 was heated to 90 ° C. 14.74 g of ethylene oxide were added and reacted until the EO was substantially consumed under a headspace of a synthesis gas of 2: 1 H ₂ : CO ratio of 1500 psi (10.3 MPa). The reactor contents were transferred to the phase separator under syngas pressure, where phase separation started immediately, separating 8.22 g of underlying material. The reaction liquid in the upper layer was recycled to the reactor. The compositions of the upper and lower layers are listed in Table 2. Catalyst compartmentalization data is shown in Table 3. The average reaction rate through this recycle was 14 g / L / hour.

Example 3

Phase separation method, recycle 2.

The reaction solution recycled from Example 2 was heated to 90 ° C. 14.74 g of ethylene oxide were added and reacted under a headspace of syngas with a 2: 1 H ₂ : CO ratio of 1500 psi (10.3 MPa). The reactor contents were transferred to a phase separator under syngas pressure, where phase separation immediately started, separating 8.05 g of underlying material. The reaction liquid in the upper layer was recycled to the reactor. The compositions of the upper and lower layers are listed in Table 2. Catalyst compartmentalization data is shown in Table 3. The average reaction rate through this recycle was 37 g / L / hour.

Example 4

Phase separation method, recycle 3.

The reaction solution recycled from Example 3 was heated to 90 ° C. 14.74 g of ethylene oxide were added and reacted under a headspace of syngas with a 2: 1 H ₂ : CO ratio of 1500 psi (10.3 MPa). The reactor contents were transferred to a phase separator under syngas pressure, where immediately phase separation began, separating 19.50 g of the underlying material. The reaction liquid in the upper layer was recycled to the reactor. The compositions of the upper and lower layers are listed in Table 2. Catalyst compartmentalization data is shown in Table 3. The average reaction rate through this recycle was 49 g / L / hour.

Example 5

Phase separation method, recycle 4.

The reaction solution recycled from Example 4 was heated to 90 ° C. 14.74 g of ethylene oxide were added and reacted under a headspace of syngas with a 2: 1 H ₂ : CO ratio of 1500 psi (10.3 MPa). The reactor contents were transferred to a phase separator under synthesis gas pressure, where phase separation started immediately, separating 32.80 g of underlying material. The reaction liquid in the upper layer was recycled to the reactor. The compositions of the upper and lower layers are listed in Table 2. Catalyst compartmentalization data is shown in Table 3. The average reaction rate through this recycle was 34 g / L / hour.

Example 6

Phase separation method, recycle 5.

The reaction solution recycled from Example 5 was heated to 90 ° C. 14.74 g of ethylene oxide were added and reacted under a headspace of syngas with a 2: 1 H ₂ : CO ratio of 1500 psi (10.3 MPa). The reactor contents were transferred to a phase separator under syngas pressure, where immediately phase separation began, separating 71.90 g of underlying material. The reaction liquid in the upper layer was recycled to the reactor. The compositions of the upper and lower layers are listed in Table 2. Catalyst compartmentalization data is shown in Table 3. The average reaction rate through this recycle was 30 g / L / hour.

The three most important results in phase separation are: 1) Achievable PDO yield rate is fast enough, 2) the majority of the catalyst is recycled (upper phase), and 3) the concentrated product (PDO) is lower phase. Was recovered.

From the PDO yield rate data of this example, it can be seen that an acceptable reaction rate was achieved and the catalyst was active even after 5 recycles (# 1).

From Table 3, it can be seen that high% catalyst was directly recycled as the top phase (# 2).

From Table 2, high PDO recovery on the bottom product and high EO recycling on the top recycle can be seen (# 3).

Phase Cleavage Primary Composition Example layer PDO wt% MTBE wt% Mass (g) EO% available One Down 59.70 18.13 12.94 *- 2 Down 47.97 16.60 8.22 *- 3 Down 45.97 19.15 8.50 *- 4 Down 47.32 21.73 19.50 7.55 5 Down 45.16 20.99 32.80 10.55 6 Down 47.50 25.78 71.90 25.06 One topside 4.74 85.70 152.36 *- 2 topside 5.15 87.16 160.04 *- 3 topside 17.67 77.60 167.19 *- 4 topside 27.31 54.86 163.47 92.45 5 topside 14.41 69.85 147.04 89.45 6 topside 10.59 80.36 93.46 74.94 Intentionally reacted until EO is completely consumed

Catalyst Partitioning Data Example layer % Available catalyst (Co; Ru) One topside 90; 88 2 topside 91; 88 3 topside 93; 91 4 topside 82; 75 5 topside 78; 71 6 topside 61; 75 One Down 10; 12 2 Down 9; 12 3 Down 7; 9 4 Down 18; 25 5 Down 21; 29 6 Down 38; 25

Example 7

Phase separation catalyst recycle / product recovery method using a catalyst prepared by a stepwise process.

2.14 g (6.90 mmol) of 1,2-bis (9-phosphacyclononyl) ethane, 0.694 g (3.25 mmol Ru) of triruthenium dodecylcarbonyl, methyl-tert- 119 g of butyl ether [MTBE] were added. The autoclave body was sealed and mounted on a bench scale processing unit. Under a headspace of a 4: 1 (H ₂ : CO) synthesis gas at 1500 psi (10.3 MPa), the mixture was equilibrated at 105 ° C. for 1 hour. To the reactor was added a solution of 1.11 g (6.50 mmol Co) of dicobalt octacarbonyl and 0.108 g (1.32 mmol) of sodium acetate in 33.3 g of MTBE at the reaction conditions. The catalyst was preformed at 105 ° C. and 1500 psi (10.3 MPa) for 1.75 hours. The reactor temperature was reduced to 90 ° C. A total of 13.2 g of ethylene oxide (EO) was added in two separate portions and reacted with the 2: 1 (H ₂ : CO) syngas feedstock until EO was substantially completely consumed. The reactor contents were transferred to a thermostatic phase separator under syngas pressure. Phase separation was equilibrated at 43 ° C. 36.8 g of the bottom phase were separated. The upper phase was recycled to the reactor. The composition of the upper and lower phases is shown in Table 4. Catalyst compartmentalization data is listed in Table 5. The 1,3-propanediol product was calculated at an average rate of 26 g / L / hour.

Example 8

Phase separation method, recirculation 1.

The reaction solution recycled from Example 7 was heated to 90 ° C. 14.74 g of ethylene oxide were added and reacted under a headspace of a 2: 1 synthesis gas that was 1500 psi (10.3 MPa). The reactor contents were transferred to a phase separator under syngas pressure. When equilibrium was reached at 43 ° C., 28.5 g of the lower phase material was separated. The upper phase reaction was recycled to the reactor. The composition of the upper and lower phases is shown in Table 4. Catalyst compartmentalization data is listed in Table 5. The average reaction rate through this recycle was 24 g / L / hour.

Example 9

Phase separation method, recycle 2.

The reaction solution recycled from Example 8 was heated to 90 ° C. 11.00 g of ethylene oxide were added and reacted under the headspace of a 2: 1 synthesis gas that was 1500 psi (10.3 MPa). The reactor contents were transferred to a phase separator under syngas pressure. When equilibrium was reached at 43 ° C., 24.8 g of the lower phase material was separated. The upper phase reaction was recycled to the reactor. The composition of the upper and lower phases is shown in Table 4. Catalyst compartmentalization data is listed in Table 5. The average reaction rate through this recycle was 35 g / L / hour.

Example 10

Phase separation method, recycle 3.

The reaction solution recycled from Example 9 was heated to 90 ° C. 11.00 g of ethylene oxide were added and reacted under the headspace of a 2: 1 synthesis gas that was 1500 psi (10.3 MPa). The reactor contents were transferred to a phase separator under syngas pressure. When equilibrium was reached at 43 ° C., 19.1 g of the lower phase material was separated. The upper phase reaction was recycled to the reactor. The composition of the upper and lower phases is shown in Table 4. Catalyst compartmentalization data is listed in Table 5. The average reaction rate through this recycle was 23 g / L / hour.

Example 11

Phase separation method, recycle 4.

The reaction solution recycled from Example 10 was heated to 90 ° C. 11.00 g of ethylene oxide were added and reacted under the headspace of a 2: 1 synthesis gas that was 1500 psi (10.3 MPa). The reactor contents were transferred to a phase separator under syngas pressure. When equilibrium was reached at 43 ° C., 38.9 g of the lower phase material was separated. The upper phase reaction was recycled to the reactor. The composition of the upper and lower phases is shown in Table 4. Catalyst compartmentalization data is listed in Table 5. The average reaction rate through this recycle was 18 g / L / hour.

Example 12

Phase separation method, recycle 5.                 

The reaction solution recycled from Example 11 was heated to 90 ° C. 11.00 g of ethylene oxide were added and reacted under the headspace of a 2: 1 synthesis gas that was 1500 psi (10.3 MPa). The reactor contents were transferred to a phase separator under syngas pressure. When equilibrium was reached at 43 ° C., 38.9 g of the lower phase material was separated. The upper phase reaction was recycled to the reactor. The composition of the upper and lower phases is shown in Table 4. Catalyst compartmentalization data is listed in Table 5. The average reaction rate through this recycle was 17 g / L / hour.

From the PDO yield rate data of this example, it can be seen that an acceptable reaction rate was achieved and the catalyst was active even after 5 recycles (# 1).

From Table 5, it can be seen that high% catalyst was directly recycled as the top phase (# 2).

From Table 4, the high PDO recovery on the bottom can be seen (# 3).

Phase Cleavage Primary Composition Example layer PDO wt% MTBE wt% Mass (g) EO% available 7 Down 63.68 16.15 24.80 7.03 8 Down 49.68 17.39 28.50 11.52 9 Down 68.08 18.03 24.80 13.45 10 Down 53.34 24.31 19.10 15.97 11 Down 33.32 19.39 38.90 22.36 12 Down 30.03 25.91 29.80 33.07 7 topside 7.20 44.63 165.07 92.97 8 topside 8.89 61.35 152.73 88.48 9 topside 36.69 48.66 139.09 86.55 10 topside 16.88 54.86 131.42 84.03 11 topside 6.14 86.65 104.92 77.64 12 topside 27.30 34.57 88.12 66.93

Catalytic Species Partitioning Data Example layer % Available catalyst (Co; Ru) 7 topside 70; 67 8 topside 82; 68 9 topside 85; 72 10 topside 89; 73 11 topside 67; 63 12 topside 73; 73 7 Down 30; 33 8 Down 18; 32 9 Down 15; 28 10 Down 11; 27 11 Down 33; 37 12 Down 27; 27

Example 13

Recirculation of cascaded bottom phase catalyst.

The lower layer samples of Examples 7 and 8, enriched with 1,3-propanediol product, were distilled to 90 to 110 ° C. under vacuum conditions of 60 to 4 mmHg. Methyl-tert-butyl ether reaction solvent and 1,3-propanediol were collected at column overhead. There was 92% more 1,3-propanediol in the overhead material. Distillation was performed to distill 75% of the initial fill mass. Ten grams of the distilled bottom sample containing the recycled catalyst, some 1,3-propanediol and a small amount of heavy bottoms were stored in an autoclave of 300 ml in an inert atmosphere drybox. 74 g of fresh methyl-tert-butyl ether reaction solvent was added to the autoclave. The autoclave was sealed and mounted on a bench scale processing unit. The catalyst solution was heated to 90 ° C. while stirring. Under the headspace of a 4: 1 (H ₂ : CO) synthesis gas, 11.00 g of ethylene oxide was added and reacted. The reactor contents were transferred to a phase separator under syngas pressure and phase separation started at 45 ° C. When equilibrium was reached, 12.6 g of the lower phase material was separated. This lower phase contained 56.47 wt% of the 1,3-propanediol product. The upper phase reaction liquid was recycled to the reactor and heated to 90 ° C. under a 2: 1 (H ₂ : CO) synthesis gas feedstock headspace. 11.00 g of ethylene oxide was added and reacted to this recycled reaction solvent. The reactor contents were transferred to a phase separator under synthesis gas pressure and phase separation started at 43 ° C. When equilibrium was reached, 24.5 g of the lower phase material was separated. This lower phase contained 45.14 wt% of the 1,3-propanediol product. The product yield of these reactions was 81%. This demonstrates that the catalyst is strong and still active after distillation from the product phase and is recycled twice through the upper phase of the subsequent reaction.

Example 14

Use of Hexane as Phase Cleavage Inducer.

In a 300 ml autoclave in an inert atmosphere drybox, 1.159 g (3.73 mmol) of 1,2-bis (9-phosphacyclononyl) ethane, 0.696 g (3.27 mmol Ru) of triruthenium dodecylcarbonyl, methyl-tert- 119 g of butyl ether [MTBE] were added. The autoclave body was sealed and mounted on a bench scale processing unit. Under a headspace of 4: 1 (H ₂ : CO) synthesis gas at 1500 psi (10.3 MPa), the mixture was equilibrated at 105 ° C. for 1.5 hours. To the reactor was added a solution of 1.13 g (6.50 mmol Co) of dicobalt octacarbonyl and 0.108 g (1.32 mmol) of sodium acetate in 33.3 g of MTBE at the reaction conditions. The catalyst was preformed at 105 ° C. and 1500 psi (10.3 PMa) for 1.75 hours. The reactor temperature was reduced to 90 ° C. 22 g of ethylene oxide (EO) was added once and reacted with a 2: 1 (H ₂ : CO) syngas feedstock. The reactor contents were transferred to a thermostatic phase separator under syngas pressure. Phase separation was equilibrated at 43 ° C. 9.746 g of the bottom phase were separated. The upper phase was recycled to the reactor. In a manner similar to the above example, additional ethylene oxide was added to the recycled upper layer to react, followed by phase cleavage by temperature. In the third recycle of this example, 11.00 g of ethylene oxide was added and reacted at 90 ° C. and 1500 psi (10.3 MPa). When transferred to the phase separator and cooled to 35 ° C., no clear phase separation occurred. When 11.00 g aliquots of ethylene oxide were added in two separate portions, and then reacted under the conditions described above and cooled to 33 ° C, 1,3-propanediol at a concentration capable of causing phase separation was not calculated. This reaction is believed to yield some byproducts such as ethanol and propanol that are virtually miscible and prevent phase separation. On the other hand, 10 g of hexane was added to the reactor under the conditions described above, and then transferred to the reactor and cooled to induce phase separation at 77 ° C. This is a way that phase disruption can be induced by changing the polarity of the system. In order to ensure a single phase reaction, it is also possible to add admixtures before or during the reaction. These admixtures can then be removed by treatment such as distillation or flash to induce phase cleavage for product recovery. After reaching equilibrium at 43 ° C., 92.7 g of the lower layer sample were separated, which contained 48% of the 1,3-propanediol product.

Claims (15)

(a) contacting a mixture of ethylene oxide, carbon monoxide, hydrogen, a non-water miscible reaction solvent and a hydroformylation catalyst composition in a reactor; (b) heating the reaction mixture to a temperature in the range of 30 to 150 ° C. at a pressure in the range of 0.7 to 27.6 MPa (100 to 4000 psi) to yield a single phase reaction product mixture containing 1,3-propanediol. ; And (c) a temperature reduction in combination with (iv) adding a phase cleavage inducing agent to the reaction product mixture to induce phase separation, (ii) first adding a miscible cosolvent to maintain the reaction product mixture as a single phase Temperature reduction in combination with the method of removing this miscible cosolvent by means of distillation or flashing; Removing miscible cosolvent by means of distillation or flashing, and (iii) adding a phase cleavage inducing agent to the reaction product mixture to induce phase separation of the reaction product mixture. Inducing phase separation in at least one method selected from the group consisting of: wherein the temperature decrease is a temperature decrease from above the freezing point of the reaction mixture to a temperature below 10 ° C. below the reaction temperature, the phase separation being a reaction solvent, catalyst composition At least 50 wt%, and a first phase comprising unreacted ethylene oxide and a second phase comprising 1,3-propanediol and residual catalyst,  Method for one step hydroformylation and hydrogenation of 1,3-propanediol. The method of one step hydroformylation and hydrogenation of 1,3-propanediol according to claim 1, wherein the second phase comprises a reaction solvent and a high molecular weight by-product. The method of one step hydroformylation and hydrogenation of 1,3-propanediol according to claim 1, further comprising physically separating the mixture of the two phases following induction of phase separation. The one-step hydroformylation of 1,3-propanediol according to claim 3, further comprising directly recycling the first phase to step (a) for further reaction with previously unreacted starting materials. And hydrogenation synthesis methods. 4. The process of claim 3, further comprising: extracting the residual catalyst from the second phase, recycling the catalyst to step (a), and sending the remaining second phase containing 1,3-propanediol to the recovery device. A method of one step hydroformylation and hydrogenation of 1,3-propanediol, further comprising the step. The process of claim 4, further comprising the steps of extracting the residual catalyst from the second phase, recycling the catalyst to step (a), and sending the remaining second phase containing 1,3-propanediol to the recovery device. A method of one step hydroformylation and hydrogenation of 1,3-propanediol, further comprising the step. 6. The one-step hydroformylation of 1,3-propanediol according to claim 5, wherein the recovery device for 1,3-propanediol is a distillation column separating the 1,3-propanediol product from the high molecular weight by-product. And hydrogenation synthesis methods. 7. The one-step hydroformylation of 1,3-propanediol according to claim 6, wherein the recovery device for 1,3-propanediol is a distillation column separating the 1,3-propanediol product from the high molecular weight by-product. And hydrogenation synthesis methods. 6. The one-step hydroformylation of 1,3-propanediol according to claim 5, further comprising the step of separating the light solvent from 1,3-propanediol, and distillation to separate into separate light solvents. Hydrogenation Synthesis Method. 7. The one-step hydroformylation of 1,3-propanediol according to claim 6, further comprising the step of separating the light solvent from 1,3-propanediol, and distillation to separate into separate light solvents. Hydrogenation Synthesis Method. The method of one step hydroformylation and hydrogenation of 1,3-propanediol according to claim 1, characterized in that the temperature during phase separation is 27 to 97 ° C. 12. The process of one step hydroformylation and hydrogenation of 1,3-propanediol according to claim 11, characterized in that the temperature during phase separation is 37 to 47 ° C. The process of claim 1 wherein the temperature during phase separation is from 27 to 97 ° C., the concentration of 1,3-propanediol is from 1 to 50 wt% of the total reaction product mixture, and the oxirane concentration is from 0.2 to the total reaction product mixture. A method for one step hydroformylation and hydrogenation of 1,3-propanediol, characterized in that 20wt%. The process of claim 13, wherein the temperature during phase separation is 37 to 47 ° C., the concentration of 1,3-propanediol is 8 to 32 wt% of the total reaction product mixture, and the oxirane concentration is from 0.2 to the total reaction product mixture. A one-stage hydroformylation and hydrogenation method of 1,3-propanediol, characterized in that 20 wt%. The process of one step hydroformylation and hydrogenation of 1,3-propanediol according to claim 9 or 10, further comprising the step of recycling the individual light solvents to step (a).

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